Aluminum dihydride from E( iv ) precursors (E = Si, Ge) and its bond-activation reactivities

A distinctive synthetic route has been demonstrated in which the aminotroponiminato (ATI)-stabilized aluminum dihydride complex (ATI)AlH2 was prepared from a (ATI)SiHCl2 precursor. (ATI)AlH2 was also isolated from aluminum(III) dichloride (ATI)AlCl2 via salt-metathesis reaction. Subsequent reaction with the ATIH ligand enabled the isolation of the N-tetracoordinated (ATI)Al(III)-complex via aluminum monohydride (ATI)AlH(ATI) intermediate. The dihydride compound was found to activate CS (in CS2) and PSe (in Ph3PSe) bonds yielding the aluminum(III) μ-sulphide and μ-selenide dimer (ATI)Al(μ-S)2 and (ATI)Al(μ-Se)2, respectively. All compounds were characterized using multinuclear NMR spectroscopy and single-crystal X-ray diffraction.